TW200918642A - Phosphorescent polymer compound and organic electroluminescent device using the same - Google Patents

Abstract

Disclosed is a phosphorescent polymer compound having high luminous efficiency and long emission life. Aldo disclosed is an organic electroluminescent device using such a phosphorescent polymer compound. Specifically disclosed is a phosphorescent polymer compound containing a structural unit derived from a compound represented by the formula (1) below. In the formula (1), L1 and L2 each represents a specific ligand, and a combination of L1 and L2 is so selected as to satisfy a specific condition. (1)

Description

200918642 IX. Description of the Invention [Technical Field of the Invention] The present invention relates to a luminescent polymer compound. More specifically, the present invention relates to a luminescent polymer compound suitable as a luminescent material for an organic electroluminescence device, an organic electroluminescence device using the compound, and the like. [Prior Art] In recent years, in order to expand the use of organic electroluminescence devices (hereinafter also referred to as "organic EL devices"), the development of materials using high-luminous-luminescence luminescent polymer compounds is active. In progress. In order to make the organic EL element particularly useful in full color display or lighting applications, in addition to the high luminous efficiency of blue or green luminescent materials and the like, it is necessary to develop a red color that enables the organic EL element to be stably driven. Or yellow luminescent material. A ruthenium complex exhibiting red or yellow luminescent light is known, and many condensed rings are known to have a condensed ring on a ligand. Among them, an organic complex containing a samarium or isoquinoline structure is used as an illuminant. The EL element is a promising illuminant because it has a particularly high luminous efficiency. Patent Document 1 discloses a polymer light-emitting material having a luminescent defect in a polymer side chain. The polymer light-emitting material is characterized in that a ligand ligand which is bonded to a β-diketone salt of a polymer main chain and which is not related to light emission is located in a ruthenium, and further supports a 2-arylquinoline relative to the ruthenium . In this polymer material, the luminescence from the yttrium complex of the luminescent moiety is considered to be -4-200918642-based electrons in the metal-arylquinoquinone ligand or the arylquinoline ligand. Migrants are derived. Patent Document 2 discloses a polymer light-emitting material having a structure of a tris(phenylquinoline) ruthenium complex in a side chain. The polymer light-emitting material exhibits red-orange luminescence, but the luminescence is considered to be derived from electron migration in the metal-phenylquinoline ligand or in the phenylquinoline ligand, and 3 phenyl quinoxanes. Any of the porphyrin ligands may be associated with luminescence. Further, Patent Document 2 discloses a polymer light-emitting material in which a phenylpyridine group bonded to a polymer main chain is bonded to ruthenium and further has two phenylquinoline structures coordinated to the ruthenium. Since the luminescent material exhibits red-orange luminescence, luminescence is believed to be caused by two phenylquinoline ligands leaving the polymer backbone. However, in the organic EL element using the luminescent material disclosed in Patent Documents 1 and 2, there is room for improvement in terms of luminous efficiency or durability. [Patent Document 1] Japanese Patent Publication No. 2004-5 3 1 8 5 (Patent Document 2) Japanese Patent Application Publication No. JP-A No. 2000-A No. The problem is to provide an organic electroluminescence device having high luminous efficiency and long life. [Means for Solving the Problems] As a result of the review of the above-mentioned problem, the inventors of the present invention conducted a review of the results of the review, and considered that it is important to reduce the luminous efficiency or the lifetime in the organic using the polymer light-emitting material. The reason is that the structure of the ruthenium complex of the high-luminescence light-emitting part participates in the luminescence; or the self-polymer chain of the ligand participating in the luminescence is easy to be combined with other light-emitting parts or charge transporters, etc. Shape, etc.; further, due to the close proximity to the physical distance of the mating substance and the element-driven extinction material participating in the luminescence, and thus by participating in the luminescent complex, in the erbium complex configuration, The main chain of the polymer compound is a ligand 'and the photoligand does not contain a hetero atom, and the organic EL element emits light and the lifetime can be increased, and the present invention has been completed. That is, the present invention relates to, for example, the following [1] to [8] ° [1] a luminescent polymer compound having a structural unit derived from a compound represented by the formula (1). The number of molecular light-emitting positions has been found to be too high to become a quasi-molecular movement. The limitation of the knot does not participate in the efficiency of the hair can be mentioned below.

(In the formula (1), L1 represents a group selected from the following formulas (al) to (each ligand, and L2 represents one selected from the group consisting of the following formulas (b1 to (b6)). [Chemical 2]

(a4) (a5) (a6) [In each of the formulas (al) to (a6), the Ra-based groups independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a carbon atom having a polymerizable functional group. A number of 1 to 5 alkyl or alkenyl groups. Further, in each of the formulas (a1) to (a6), one of Ra represents an alkyl group or an alkenyl group having 1 to 5 carbon atoms having a polymerizable functional group as described above) 200918642 [Chem. 3]

[In each of the formulae (b1) to (b6), Rb each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms]. However, 'L1 and L2' are selected from the following: E1 and E2 below satisfy the relationship of E^E2. Ε1 ' represents a solution of a ruthenium complex represented by the following formula (2) [when the optical path length is 1 cm, the absorbance of monochromatic light at a wavelength of 305 nm can be obtained in a dichloromethane solution prepared by 〇.1 2 5 ° C measured], in the luminescence spectrum excited by a monochromatic light with a wavelength of 3 5 Onm, the vibration number of the light showing the maximum luminous intensity (cnT1); -8 - 200918642

[In the formula (2), L1 represents l1 in the above formula (i), which is selected from one of the above formulas (al) to (a6), and all of the above Ra are coordinated by a hydrogen atom. child]. E2 is a solution of a ruthenium complex represented by the following formula (3) [when the optical path length is 1 cm, the absorbance of monochromatic light at a wavelength of 350 nm can be 0.1 in a dichloromethane solution prepared at 25 ° C. The next measurement] shows the vibration number (cnT1) of the light having the maximum luminous intensity in the luminescence spectrum excited by the monochromatic light having a wavelength of 3 5 Onm. [Chemical 5]

(3) In the formula (3), L2 is L2 in the above formula (1), which is selected from one of the above formulas (b1) to (b6), and all of the above Rb are hydrogen atoms. Matching seat]). [2] The photoluminescent polymer compound of [1], wherein the polymer compound obtained by base polymerization from 200918642 is a saturated carbon chain skeleton. [3] The luminescent polymer compound according to [1], wherein the difference between the above E! and the above E2 is 100 or more. [4] The luminescent polymer compound according to [1], wherein the luminescent polymer compound further contains at least one of a polymerizable compound having a hole transport property and a polymerizable compound having electron transport properties. Derived structural unit. [5] A method for producing an organic electroluminescence device, comprising the step of forming an organic compound layer containing at least one layer of any of the photoluminescent polymer compounds of [1] to [4] on an anode, And a step of forming a cathode on the organic compound layer. [6] An organic electroluminescence device comprising: a pair of electrodes; and an organic compound layer containing at least one of the light-emitting layers between the electrodes, wherein the light-emitting layer contains [1] to [4] One of the light-emitting polymer compounds. [7] An organic electroluminescence device characterized in that it is produced according to the manufacturing method of [5]. [8] A display device characterized by using the organic electroluminescence element of [6] or [7]. [Effects of the Invention] The organic EL element using the luminescent polymer compound of the present invention is particularly excellent in luminous efficiency and life. -10-200918642 [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be specifically described. "Silver-emitting polymer compound" <Silver-emitting site> The phosphorescent polymer compound of the present invention contains a photoluminescent compound represented by the following formula (1) ) derived structural units. [Chemical 6]

In the above formula (1), L1 represents one of the following formulas (al) to (a6), and L2 represents one of the following formulas (b1) to (b6). -11 - 200918642 [化7]

(a4) (a5) (a6) (In each of the formulas (al) to (a6), the Ra-based groups independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a carbon atom having a polymerizable functional group. Further, in each of the formulae (al) to (a6), one of Ra represents a carbon atom number of 1 to 5 having a polymerizable functional group as described above. Alkyl or alkenyl). -12- 200918642 [化8]

Rb Rb (b1)

(b2)

(b4) (b5) (b3)

(In each of the formula (b1) to the atom or the carbon atom g (b6), Rb each independently represents an alkyl group of hydrogen 1 to 10). The compound represented by the above formula (1) has two different types of & L and L2', each having one or two ruthenium complexes. L1 is a ligand derived from the above formulas (al) to (a6), and L2 is selected from the above-mentioned ligands represented by $( Μ >~(b6 ). Since L1 is in the structure of the ligand Containing a salivary D or isoquinoline skeleton, the ruthenium complex can exhibit luminescence in a visible light region of a longer wavelength such as red or yellow. Further, in L1, all of Ra in the above formulas (al) to (a6) are hydrogen atoms. When the optical path length is -13 to 200918642 lcm, the absorbance of the monochromatic light at a wavelength of 350 nm can be 0.1 in a 0.1 methylene chloride solution prepared by the following formula (2). C measurement], in the luminescence spectrum excited by monochromatic light having a wavelength of 550 nm, when the vibration number (cnT1) of the light showing the maximum luminescence intensity is E1, L1 is (al), (a2), ( E1 at a3), (a4), (a5) or (a6), each being 18692cm·1, 1 824 8 cm·1, 1 6807cm·1, 1 675 0cm·1, 1 6077cm.1 and 15 175cm· 1.

On the other hand, in the case where all of Rb in the above formulas (b1) to (b6) are hydrogen atoms in L2, a solution of the ruthenium complex represented by the following formula (3) [when the optical path length is 1 cm, at a wavelength of 350 nm The absorbance of monochromatic light can be measured in a dichloromethane solution prepared in 〇.1, measured at 25t], and the vibration of light showing the maximum luminescence intensity in the luminescence spectrum excited by monochromatic light having a wavelength of 350 nm When the number (cnT1) is E2, L2 is E2 at (bl), (b2), (b3), (b4), (b5) or (b6), each being 1 9493 cm·1, 1 8692 cm·1, 1 8248cm'1, 1 6807cm*1, 1 6750cm·1 and 1 6077CHT1. -14- 200918642 [化10]

(3) Here, the absorbance or luminescence spectrum of the above-mentioned ruthenium complex solution is obtained by using a usual ultraviolet-visible absorption spectrophotometer or a fluorescence spectrophotometer. In the present invention, the ultraviolet-visible absorption spectrophotometer is UV-2400PC manufactured by Shimadzu Corporation, and the fluorescent spectrophotometer is FP6500 manufactured by JASCO Corporation. Further, in the luminescence spectrum of the ruthenium complex solution, the maximum vibration intensity indicates the number of vibrations (unit: cnT1), and if it is a thin solution, it does not depend on the concentration of the ruthenium complex. The concentration is such that the absorbance of monochromatic light having a wavelength of 350 nm at a wavelength of 1 cm is 0·1, and if the absorbance is 2 or less, it is regarded as a thin solution. In the above L1 and L2, E1 and E2 are selected from the relationship that satisfies Ei<E2. When the relationship between E and E2 is such a relationship, the luminescent polymer compound containing the structural unit derived from the oxime complex represented by the above formula (1) is expressed by the above formula (2). The solution of the complex compound [when the optical path length is 1 cm, the absorbance of the monochromatic light at a wavelength of 350 nm can be measured in 0.1 methylene chloride solution, measured at 25 ° C], and the luminescent color is almost the same. . Therefore, regarding the luminescence of the above-mentioned luminescent polymer compound, it is considered that only the ligand L1 participates, and the ligand L2 does not participate; that is, only the ligand L1 emits light, and the ligand L2 does not emit light- 15-200918642 In the fluorene-emitting polymer compound having a structure derived from the ruthenium complex represented by the above formula (1), the ligand which participates in luminescence is a structure which tends to be a complex, and a luminescent polymer The combination of the main chain (L 1 ), the EL element using the compound represented by the above formula (1), has a high luminous efficiency and a long life compared to the conventional narrow element. . In particular, the difference between the above E! and the above E2 is as defined in the case of the mono-light-emitting polymer compound derived from the ruthenium complex represented by the above formula (1) in the case of lcnOOcnT1, and it is presumed that the participation in the luminescence is completely limited to For L1, the luminous effect of the organic EL element has a longer life. In the fluorene-emitting polymer compound having a structure derived from the oxime complex represented by the above formula (1), the ligands L 1 and L2 do not contain a hetero atom directly other than the nitrogen atom of the metal. It is presumed that the electrons due to the isolated electron pair contained in the yttrium complex or the important reason for the decrease in the efficiency of the interaction with the positively charged matting substance such as metal ions are suppressed, compared to the conventional EL element. In other words, the narrow element of the present invention using the luminescent polymer compound containing the erroneous structure unit represented by the above formula (1) can have a longer life. The above formula (1), for example,

When the unit is formed by the EL of the compound, the position of the 燐 position can be changed to the unit. The aromatic ring is thereby pulled out and emitted by the organic matter. EL -16- 200918642 [Chem. 11]

When h2c-c-R^L is expressed, the structural unit derived from the above-mentioned ruthenium complex is as follows. [v 12] fv

[Ra] Each of the above formulas (al) to (a6) independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 5 carbon atoms having a polymerizable functional group. The base or alkenyl group, the luminescent color of the luminescent compound of the present invention-17-200918642, is not affected by the type of the substituent. For example, in the compound represented by the above formula (1), L1 is a ligand represented by the above (a4), L2 is a ligand represented by (b1), and a series of the following ruthenium complexes (1 A) ~(1 D ) The luminescent color of the polymer obtained by radical polymerization [when the optical path length is 1 cm, the absorbance of monochromatic light at a wavelength of 350 nm can be measured in a methylene chloride solution of 0.1 at 25 t. ], no matter which is in the XYZ color system of the International Commission on Illumination (CIE), the xy coordinates are in the range of (X, y) = (0_61 ± 0·01, 0.39 ± 0.01), almost the same orange color. Further, the luminescent color is a solution of the ruthenium complex represented by the above formula (2), that is, the above L1 is a complex represented by the above (a4) (when the optical path length is 1 cm, at a wavelength of 305 nm) The illuminance of the monochromatic light can be measured in a 0.1 methylene chloride solution at 25 ° C. The illuminating color system is almost the same, as described above. That is, the luminescent color of the luminescent polymer compound containing the structural unit derived from the following erbium complexes (1 A ) to (1 D ), and L1 in the above formula (2) are the above (a4) a solution of the complex of the complex of the ligand (the absorbance of the monochromatic light at a wavelength of 350 nm can be measured at 25 ° C in 0.1 prepared dichloromethane solution) when the optical path length is 1 cm. Color, almost the same. -18- 200918642 [Chem. 13]

(1B)

The above alkyl group having 1 to 10 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an octyl group or a fluorene group. Base. Among the above-mentioned formulas (a1) to (a6), one of Ra is an alkyl group or an alkenyl group having 1 to 5 carbon atoms and having the above polymerizable functional group. The polymerizable functional group may be any of radical polymerizable, cationic polymerization -19-200918642, anionic polymerizable, additional polymerizable, and condensation polymerizable functional groups. Among them, the radical polymerizable functional group is preferably produced by the production of a polymer. The polymerizable functional group may, for example, be an alkenyl group (vinyl group, isopropenyl group, allyl group, etc.), a styryl group, an acryloyloxy group, a methacryloxy group, or a methacryloxy group. A urethane (meth) acryloyloxy group such as a benzyl ethyl carbamate group, a vinyl fluorenyl group, a derivative thereof, or the like. Among them, a vinyl group, a styryl group, and a methacryloxy group are preferred. An alkyl group having 1 to 5 carbon atoms having the above polymerizable functional group, specifically, an alkyl group including a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group or the like The atom is a group substituted with the above polymerizable functional group. Further, a divalent group (spacer) containing a hetero atom such as _〇_, -0-CH2- or the like may be incorporated between the alkyl group and the polymerizable functional group. The alkyl group or the alkenyl group having 1 to 5 carbon atoms of the above-mentioned polymerizable functional group is a group represented by the following chemical formulas (cl) to (c8). -20- 200918642 [Chem. 14]

Factory (cl)

The above Ra is preferably a hydrogen atom, a methyl group or a t-butyl group, respectively. Specifically, in the above formulae (al) to (a6), in the above formulae (al) to (a6), Ra having an alkyl group or an alkenyl group having 1 to 5 carbon atoms of the polymerizable functional group is hydrogen. Atom is preferred. [Rb] Among the above formulae (b1) to (b6), 'Rb' represents an illuminating color of the mercaptoluminescent polymer compound of the present invention, which is independently a hydrogen atom or a fluorenyl group having 1 to 10 carbon atoms. And is not affected by this heavy stomach. An alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, cyclohexyl-21 - 200918642, Xinji, Yanji and so on. Among them, a hydrogen atom, a methyl group, and a t-butyl group are preferred. Specifically, based on the efficiency or the lifetime of the organic EL device, the ligands represented by the above formulas (b1) to (b6) are each a ligand represented by the following formulas (b1) to (b6'). For the best.

(b4,) (b5,) (b6') Among the above formulae (b1) to (b6'), each of the RV systems is independently a methyl group, a t-butyl group or a hydrogen atom, and at least one of them Rb1 is methyl or t-butyl. -22- 200918642 [Manufacturing method of the ruthenium complex represented by the formula (1)] The ruthenium complex represented by the above formula (1) can be produced according to a conventional method', for example, according to the following step (i)~ (制造): Step (i): in the ligand L2 of the ruthenium complex represented by the above formula (1), a substituent on a carbon atom to which a ruthenium atom is bonded, and a hydrogen atom The ligand (L2-H) and ruthenium chloride trihydrate (irci3(H20)3) are reacted to produce a compound of the following formula (a compound represented by 〇〇; and step (ii): the above formula (1) In the ligand L 1 of the ruthenium complex, the substituent on the carbon atom to which the ruthenium atom is bonded, and the ligand (L1-!!) as a hydrogen atom and the following formula (α) A step of reacting a compound in the presence of silver trifluoromethanesulfonate to produce a complex represented by the above formula (1).

(0!) (In the formula (α), the L2 system is synonymous with L2 in the above formula (1)). <Charge transporting portion> The luminescent polymer compound of the present invention may further contain at least one of a polymerizable compound having a hole transporting property of -23 to 200918642 and a polymerizable compound capable of transporting electrons. Construction unit. Further, in the present invention, a polymerizable compound having a hole transport property and a polymerizable compound having electron transport properties are also referred to as a charge transporting polymerizable compound. The luminescent polymer compound is preferably a structural unit derived from one or more kinds of polymerizable compounds having a hole transporting property, or one or two or more kinds of electron transporting polymerizable compounds. A polymer compound derived from a structural unit. When such a polymer compound is used, since the degree of mobility of the charge in the light-emitting layer is high and it can be applied to form a homogeneous film, higher luminous efficiency can be obtained. In addition, the light-emitting polymer compound further preferably contains one or two or more kinds of structural units derived from a polymerizable compound having a hole transporting property, and one or two or more kinds of electron transporting polymerizations. A polymer compound of a structural unit derived from a compound. When such a polymer compound is used, since the polymer compound has a function of hole transporting property and electron transporting property, it is possible to improve efficiency by holes and electrons in the vicinity of the photoluminescent polymer compound of the present invention. The recombination is carried out, so that a high luminous efficiency can be obtained. The polymerizable compound of the above-mentioned hole transporting property and the polymerizable compound of the above electron transporting property are not particularly limited, except for the substituent having a polymerizable functional group, and a conventional charge transporting compound can be used. Conventional charge transporting compounds, for example, a hole transporting compound such as a triarylamine derivative or a carbazole derivative, or an oxadiazole derivative, a triazole derivative, an imidazole derivative, a triazine derivative, or a triaryl group. Borane derivatives and the like - 24 - 200918642 sub-transporting compounds. The polymerizable functional group may be any of a radical polymerizable property, a cationic polymerizable property, an anionic polymerizable property, an additional polymerizable property, and a condensation polymerizable functional group. Among them, a radical polymerizable functional group is preferred, and the polymer is preferably produced. The above polymerizable functional group, for example, an alkenyl group (vinyl group, isopropenyl group, allyl group, etc.), a styryl group, an acryloyloxy group, a methacryloxy group, a methacryloxy group A urethane (meth) acryloyloxy group, a vinyl decylamino group, a derivative thereof, or the like of a benzyl ethyl carbamate group or the like. Among them, vinyl, styryl and methacryloxy groups are preferred. More specifically, when the polymerizable functional group is an alkenyl group, the substituent having the above polymerizable functional group is more preferably a substituent represented by the following general formulas (A1) to (A12). Among them, the substituents represented by the following formulas (A1), (A5), (A8), and (A12) are preferable because the polymerizable functional group can be easily introduced into the charge transporting compound. -25- 200918642

——ch2 H2C—ch2

The polymerizable compound of the above-mentioned hole transport property is specifically a compound represented by the following general formulas (E1) to (E6), and is based on the charge shift in the non-conjugated polymer compound of -26-200918642. From the viewpoint of the degree, a compound represented by the following formulas (El), (E2) and (E6) is more preferable. [Chem. 18]

The compounds represented by the formulae (E1) to (E6) may each have a substituent other than a hydrogen atom on the aromatic ring, such as a halogen atom, a cyano group, a carbon number of ^~^, and a carbon number of 6 to 1Q. The base group, the oxy group having 1 to 1 carbon atoms, and the alkyl group having 1 to 10 carbon atoms are substituted as a substituent, and may have a methyl group. Specifically, the electron transporting polymerizable compound is preferably a compound represented by the following general formulas (E7) to (E15), and is based on a high charge mobility in the non-conjugated polymer compound. The viewpoint is that the compound represented by the following formulas (E7) and (E12) to (E14) is more preferable -27- 200918642 [Chem. 19]

(E9) (E7)

(E8)

¢13)

0E15) A compound represented by the formula (E7) to (E15), each of which may have a substituent other than a hydrogen atom on the aromatic ring, such as a halogen atom, a cyano group, a carbon number of 1 to 28-200918642 10, carbon The aryl group having 6 to 10 Å, the alkoxy group having 1 to 1 carbon atom, and the group having 1 to 10 carbon atoms are substituted as a substituent, and may have a methoxyalkyl group. Further, in the above formulae (E1) to (E15), a compound substituted with a substituent represented by the above formula (a2) to (A12), which is a substituent represented by the above formula (A1), is preferable. However, a compound having a substituent represented by the above formulas (A1) and (A5) is preferred because the functional group is easily introduced into the polymerizable compound. In the above, the compound represented by any one of the above formulas (E1) to (E3) is used as the above-mentioned hole transporting polymerizable compound, and the above (E7) and (E12) to (E14) The compound represented by any of them is more preferably used as the electron transporting polymerizable compound. When such a polymerizable compound is used, it is possible to recombine holes and electrons more efficiently on the luminescent polymer compound to obtain higher luminous efficiency. Further, at the same time as the luminescent compound, an organic EL element which can form a uniform distribution of the organic layer and has excellent durability can be obtained. &lt;Silver-emitting polymer compound&gt; The luminescent polymer compound of the present invention may be a so-called oligomer compound or a polymer compound. The weight average molecular weight of the above photoluminescent high molecular compound is preferably from 1,000 to 5,000,000', more preferably from 2,000 to 1,000,000, most preferably from 3,000 to 100,000. The molecular weight in the present specification means a polystyrene-equivalent molecular weight measured by a GPC (Gel Penetration Chromatography) method. When the above molecular weight is in the range of -29 to 200918642, the polymer is preferred because it is soluble in an organic solvent and a uniform film can be obtained. When the ratio of the ruthenium complex and the charge transporting polymerizable compound (polymerizable property of hole transporting property and/or electron transporting property) is appropriately set, the desired polymer compound can be obtained, and the desired polymer compound can be obtained. The polymer compound may be any of a random copolymer, a block copolymer, and an interactive copolymer. In the above polymer compound, the number of structural units derived from the above-described ruthenium complex is m 'charge transporting compound-derived structural unit (transport-forming polymerizable compound and/or electron transporting polymerizable compound derivative) When the total number of structural units is η (m, η represents an integer of 1 or more), the ratio of the number of structural units derived from the above-mentioned oxime complex to the total structural unit number, that is, m/( m + n ) The range of 0.001 to 0.5 is preferably 0.001 to 0.2, more preferably 0.001 to 0.2. When m/( m + n ) is in this range, an organic EL device having a high charge mobility and a small influence of concentration extinction and having high luminous efficiency can be obtained. Further, when the polymer compound contains a structural unit derived from a hole transporting compound and a structural unit derived from an electron transporting compound, the number of structural units derived from the hole transporting compound is X, and the electron transporting compound is derived. When the number of structural units is y (X and y represent an integer of 1 or more), a relationship of n = x + y is established between the η and η. The ratio of the number of structural units derived from the hole transporting compound to the number of structural units derived from the charge transporting compound x/n, and the ratio of the number of structural units derived from the electron transporting compound y/n, It is determined according to the charge transport energy of each unit -30-200918642, the charge transportability of the structural unit derived from the ruthenium complex, and the concentration. When the polymer is used as the only compound forming the light-emitting layer of the organic EL element, the range of x/n and y/n is preferably in the range of 〇_〇5 to 0.95, and is 0.20 to 0.80. The range is better. In addition, here, x/n + y/n=1 is established. Further, the "light-emitting polymer compound" may further contain structural units derived from other polymerizable compounds within the scope of the purpose of the present invention. Examples of such a polymerizable compound include a compound having no charge transporting property such as alkyl (meth)acrylate such as methyl acrylate or methyl methacrylate, styrene or a derivative thereof, but are not limited to this range. . The polymerization method of the above polymer compound is preferably carried out by radical polymerization. Therefore, the preferred method for producing the polymer compound of the present invention is a method for polymerizing at least the compound represented by the above formula (1) in the presence of a radical polymerization initiator; at least the above The compound represented by the formula (1) and the above-mentioned hole transporting polymerizable compound of x mole and/or the electron transporting polymerizable compound of y mole are polymerized in the presence of a radical polymerization initiation group. The manufacturing method (only, m, X, and y, each of which is an integer of 1 or more; m/ ( m + x + y ), preferably 〇.〇〇1 to 〇·5, more preferably 0.00 1 〜0.2 ; X / ( x + y) and y / ( x + y), each of which is preferably 0.05 to -31 - 200918642 0.95, more preferably 0.20 to 0.80). The radical polymerization initiation is carried out, for example, dimethyl-2,2'-azobis(2-methylpropionate). <<Organic EL element and its manufacturing method>> An example of the constitution of the organic EL device of the present invention is as shown in Fig. 1, but the configuration of the organic EL element of the present invention is not limited thereto. In Fig. 1, between the anode (2) and the cathode (6) disposed on the transparent substrate (1), a hole transport layer (3), a light-emitting layer (4) and an electron transport layer (5) are sequentially disposed. . In the above organic EL device, for example, either one of the hole transport layer/light emitting layer and 2) the light emitting layer/electron transport layer may be provided between the anode (2) and the cathode (6). In addition, it is also possible to provide only one of the following layers: 3) a layer containing a hole transporting material, a luminescent material, an electron transporting material, 4) a layer containing a hole transporting material, a luminescent material, 5) a luminescent material, an electron a layer of the transport material, 6) the above-mentioned light-emitting layer. Further, it is also possible to laminate two or more light-emitting layers. Among the above, the organic compound layer having the calender light-emitting polymer compound of the calender light-emitting portion and the charge transporting portion can be used as a light-emitting layer having both hole transporting property and electron transporting property. Therefore, there is an advantage that an organic EL element having high luminous efficiency can be produced without providing a layer made of another organic compound material. &lt;Substrate&gt; -32-200918642 Further, the substrate of the organic EL device of the present invention preferably uses an insulating substrate which is transparent to the light-emitting wavelength of the above-mentioned light-emitting material. Specifically, in addition to glass, PET can be used. (Polyethylene terephthalate), transparent plastics such as polycarbonate. &lt;Manufacturing Method of Organic Compound Layer&gt; The method for producing the organic compound layer is not particularly limited, and may be produced, for example, as follows. First, a solution in which a photoluminescent high molecular compound and a charge transporting polymerizable compound are dissolved is prepared. The solvent to be used in the preparation of the above-mentioned solution is not particularly limited, and examples thereof include a chlorine solvent such as chloroform, dichloromethane or dichloroethane, an ether solvent such as tetrahydrofuran or anisole, toluene or xylene. The aromatic hydrocarbon solvent, a ketone solvent such as acetone or methyl ethyl ketone, or an ester solvent such as ethyl acetate, butyl acetate or ethyl cellosolve acetate. Next, the thus prepared solution ' is formed into a film by using an inkjet method, a spin coating method, a dip coating method or a printing method on the substrate. The concentration of the above solution depends on the compound to be used, the film formation conditions, and the like. However, for example, in the spin coating method or the dip coating method, it is preferably 〇·1 to 1 〇wt%. As described above, since the organic layer can be easily formed into a film, the manufacturing process can be simplified, and the size of the element can be increased. (Other Materials) The above-mentioned respective organic compound layers may be formed by mixing a polymer material with a binder. Examples of the polymer material include polymethylmethyl propyl-33-200918642 enoate, polycarbonate, polyester, polyfluorene, and polyphenylene oxide. Further, the materials used in the above layers may be mixed with functionally different materials such as luminescent materials, hole transporting materials, electron transporting materials, etc. to form respective layers. Even in the organic compound layer containing the above-mentioned luminescent polymer compound, it is possible to further contain other hole transporting materials and/or electron transporting materials for the purpose of complementing the charge transporting property. Such a transport material may be a low molecular compound or a polymer compound. A hole injection layer may also be provided between the anode and the light-emitting layer 'for the purpose of alleviating the injection barrier during hole injection'. In order to form the above-mentioned hole injection layer, a mixture of copper phthalocyanine, polyethylene dioxythiophene (PEDOT) and polystyrene sulfonate (PSS), oxides of molybdenum oxide or cerium oxide, fluorine may be used. A well-known material such as carbon. An insulating layer having a thickness of 0.1 to 10 nm may be provided between the cathode and the electron transporting layer or between the organic compound layers laminated adjacent to the cathode and the cathode in order to enhance electron injection efficiency. In order to form the above insulating layer, a conventional material such as lithium fluoride, sodium fluoride, magnesium fluoride, magnesium oxide or aluminum oxide can be used. a hole transporting material forming the above-mentioned hole transporting layer or a hole transporting material mixed in the light emitting layer, for example, TPD (n,N,-dimethyl-N,N,-(3-methylphenyl)) -1,ι,_biphenyl-4,4,diamine); a-NPD (4,4,-bis[N-(1-naphthyl)-N-phenylamino]biphenyl); a low molecular triphenylamine derivative such as m-MTDATA (4,4',4''-tris(3-methylphenylphenylamino)triphenylamine): polyvinylcarbazole; polymerization The polymerizable compound is introduced into the polymer compound obtained by the derivative of the above-mentioned triphenylamine; and the fluorescent light-emitting polymer compound such as poly(p-phenylene) is used.上-34 - The polymer compound, the triphenylamine skeleton can be used alone or in combination with a hole transporting material, and the conductivity of the transport layer in the hole can be used, etc. 200918642 For example, there is a special opening 8-15. 75, 75, pp. The above-mentioned electric sputum transport can be used in combination of two or more types or the thickness of the hole transport layer, and it is not possible to know the same, but lnm~5μιη' is more preferably 5nm~_, and the best is ideal. The electron transporting material forming the electron transporting layer or the electron transporting material in the mixed layer may be, for example, a metal complex of a quinolol derivative such as Alq3 (tris(8-hydroxyquinoline) or a oxadiazole derivative. a low molecular compound such as a derivative, an imidazole derivative, a triazine derivative or a triaryl derivative; a polymer compound obtained by introducing a polymerizable substituent into a low molecular compound and polymerized, etc. The above high fraction, for example, has a special opening The poly-PBD disclosed in the publication No. 10-i 665 describes that the electron transporting material can be used alone or in a mixture of two or more types or by using a different electron transporting material. The electron transport thickness is dependent on the electrons. The conductivity of the transport layer may be, in other words, preferably from 1 nm to 5 μm, more preferably from 5 nm to Ιμιη, and is preferably from 1 nm to 500 nm. Further, based on suppression near the cathode side of the light-emitting layer, The hole layer and the electrons and electrons are efficiently reused in the light-emitting layer, and the hole block layer may be provided. The triazole derivative and the oxadiazole derivative are used for forming the hole block. Phenanthroline Materials and the like. The disclosed materials, due to the different lines according to a preferred system 5 0Onm emitting oxazoline) aluminum, tris yl drop firing son above compounds and the like. The method of using the layer to be used together is the best, and the layer of the combination is used. It is known that the film formation method of the hole transport layer and the electron transport layer of the -35-200918642, for example, in addition to resistance heating evaporation method, electron beam steaming In addition to the dry film forming method such as plating or sputtering, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a rod coating method, a roll coating method, or a ring-rod method can be used. Wet film forming methods such as a coating method, a dip coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, and an inkjet printing method. In the case of a low molecular compound, a dry film formation method is preferred. For example, in the case of a tubular molecular compound, a wet film formation method is preferred. &lt;Anode and cathode substrate material and method for producing the same&gt; The anode material used in the organic EL device of the present invention is preferably, for example, IT 0 (indium tin oxide), tin oxide, zinc oxide, polythiophene, or polypyrrole. A conventional transparent conductive material such as a conductive polymer such as polyaniline. The surface resistance of the electrode formed of the transparent conductive material is preferably 1 to 50 Ω/□ (ohm/square). The thickness of the anode is preferably 50 to 300 nm. The cathode material used in the organic EL device of the present invention is preferably, for example, a metal such as Li, Na, K or Cs; a metal such as Mg, Ca or Ba; A1; MgAg alloy; A1 of AlLi, Aica, etc. A conventional cathode material such as an alloy of an alkali metal or an alkaline earth metal. The thickness of the cathode is preferably 10 nm to Ιμηη, more preferably 50 to 500 nm. When a highly active metal such as an alkali metal or an alkaline earth metal is used, the thickness of the cathode is preferably from 0. 1 to 100 nm, more preferably from 0.5 to 50 nm. Further, in this case, based on the purpose of protecting the above-mentioned cathode metal, a metal layer which is stable to the atmosphere may be laminated on the cathode -36-200918642. The metal forming the above metal layer is, for example, Al, Ag, Au, Pt, Cu, Ni, Cr or the like. The thickness of the metal layer is preferably 10 nm to Ιμηι, more preferably 50 to 500 nm. Further, the film forming method of the anode material may be, for example, an electron beam vapor deposition method, a sputtering method, a chemical reaction method, a coating method, or the like, and the film forming method of the cathode material may be, for example, a resistance heating vapor deposition method or an electron beam. A vapor deposition method, a sputtering method, an ion plating method, or the like. <<Use of Organic EL Element>> The organic EL element of the present invention is preferably used as a matrix method or a segment mode pixel on a screen display device by a conventional method. Further, the above organic EL element is also suitable as a surface light source without forming a pixel. Specifically, the organic EL device of the present invention can be preferably used for displays, backlights, electronic photographs, illumination sources, recording light sources, exposure light sources, reading light sources, signs, billboards, interiors, optical communication, and the like. [Examples] Hereinafter, the related embodiments of the present invention will be described in further detail, but the present invention is not limited to the scope thereof. Further, the analysis of the polymer compound was carried out in the following manner. (1) Molecular weight The gel permeation chromatography (GPC) apparatus was carried out under the following conditions -37-200918642. Column: Shodex KF-G + KF804L + KF 8 02 + KF801 Dissolution: Tetrahydrofuran (THF)

Temperature: 40 ° C Detector: RI (Shodex RI-71) (2) Composition analysis W-NMR and 13 C-NMR measurement were carried out under the following conditions. Device: JNM EX270 67.5MHz Solvent: Heavy chloroform (CDC13) ICP elemental analysis was carried out under the following conditions. Apparatus: ICPS 8000 Mass Analysis (ESI) manufactured by Shimadzu Corporation was carried out under the following conditions. Apparatus: LCQ Advantage flowing solvent manufactured by Thermoquest: acetonitrile (0 · 5 m 1 / m i η ) In addition, the maximum external luminance and luminance half-life of the obtained element were measured by the following method. (3) Maximum external quantum efficiency (%) The organic EL element produced was placed in a dark place, and a spectroradiometer (CS-1 000T 'Konica Minotata Co., Ltd.) was placed in a vertical direction with respect to the light-emitting surface. 100cm apart in the direction. The predetermined voltage was applied to the organic light-emitting device for 1 second to emit light, and measured by a field of view of 2 degrees: current 通电 energized on the device, front luminance observed by the anode side of the device - 38 - 200918642 and luminescence spectrum . The applied voltage starts from ον and rises stepwise with a difference of 〇 · i V , and then measures the current 値, brightness, and luminescence spectrum after the voltage is increased. The maximum external quantum efficiency is calculated from the measured enthalpy, and the highest enthalpy is used as the luminescence external quantum efficiency of the element. (4) The highest brightness of arrival (cd/m2) is measured in the same manner as the maximum external quantum efficiency described above except that the applied voltage is increased by 0_5 V, and the front luminance of the produced organic light-emitting element is measured and measured. The highest 値 is the highest reaching brightness of the component. (5) Luminance halving time (h) Similarly to the measurement of the maximum external quantum efficiency described above, the front luminance of the produced organic light-emitting device was measured, and the luminance was applied to the device to have a luminance of 10 cd/m2. The photodiode of the photodiode is measured to be in close contact with the anode side of the element, and the photocurrent of the photodiode is measured by a certain current on the element, and the photocurrent is half time as the luminance halving time [ Synthesis Example 1] Synthesis of a ligand (UH) and a ligand (L2-H) (Synthesis Example 1-1: Synthesis of Compound (a2-lH)) -39- 200918642 [Chem. 20]

OHC

Ph3PCH3Br / BunLi

(b2-1 -H) 4.6 g (13 mmol) of methyltriphenyllithium bromide was suspended in 25 ml of tetrahydrofuran, and 8.1 ml of a 1.6-inch hexadecyl solution of n-butyllithium was added dropwise at 〇 ° C (1 3 Mmo 1). After stirring for 1 hour at the same temperature, 2.6 g (13 mmol) of 4-methyl-bromobenzo[h]porphyrin (synthesized according to the method described in Journal of the American Chemical Society, 1945, 67, 511). The solution of 15 ml of tetrahydrofuran was added dropwise and stirred at room temperature for 3 hours. The solvent was distilled off from the obtained reaction liquid under reduced pressure, and purified by column chromatography (solvent: chloroform) of hydrazine gel to obtain compound (a2-lH) 2.3 g (ll mmol) ( Yield 85%). (Synthesis Example 2: Synthesis of Compound (a3-l-H)) [Chem. 21] (HO) 2B^0&gt;-CN PdIPPhj), 2) HCI aq.

(P3) (a3-l-H)

TfzO

OH N£t3 -40 - 200918642 5.0 g (34 mmol) of 3-hydroxyisoquinoline was dissolved in 40 ml of methylene chloride. The solution was cooled in an ice bath, followed by dropwise addition of triethylamine 4.0 g (40 mmol) and trifluoromethanesulfonic anhydride 1 g (3 6 m m ο 1 ). After stirring at room temperature for 6 hours, the reaction mixture was washed with water and a 1N aqueous solution of hydrochloric acid, and the solvent was evaporated under reduced pressure to give a crude product of compound (P1). Next, to the obtained compound (P 1 ), 5.0 g (34 mmol) of 4-cyanophenylboronic acid, tetrakis(triphenylphosphine)palladium l.〇g (0.87 mmol), and 1,2-dimethyl were added. A 100 ml aqueous solution of 100 mmol of oxyethane and 20.7 g of potassium carbonate (195 mmol) was heated under reflux for 4 hours. The resulting reaction mixture was cooled to room temperature and the organic layer was extracted with ethyl acetate. The solvent is distilled off from the extract under reduced pressure, and then dissolved in a 1:1 mixture of dichloromethane and ethyl acetate, and passed through a short column of a hydrazine gel to obtain a crude product of the compound (P 2 ). Things. Next, the obtained compound (P2) was dissolved in 30 ml of tetrahydrofuran, and a 1.0 M diethyl ether solution of 4-vinylbenzylmagnesium chloride was added dropwise thereto, and the mixture was stirred at room temperature for 4 hours. After the 1N aqueous solution of hydrochloric acid was added to the obtained reaction mixture, the organic layer was washed with water, and the solvent was evaporated under reduced pressure to give a crude product of compound (P3). Next, 500 ml of potassium carbonate 45 g (330 mmol) of diethylene glycol and 15 g (300 mmol) of hydrazine hydrate were added to the obtained compound (P3), and the mixture was stirred under heating at 120 ° C for 2 to 5 hours. Then, the distillate was removed by heating at 200 ° C, and then cooled to room temperature. After adding water to the obtained reaction mixture, the resulting precipitate is washed with water, dried under reduced pressure, and then purified by a column chromatography method (41-200918642 column chromatography (solvent: chloroform) to obtain a compound (a3). -l -H ) 2.9 g (8.6 mmol) (yield 27%). (Synthesis Example 1-3: Synthesis of Compound (a5-l-H)) [Chem. 22]

Pd(PPh3)4K2C〇3 aq.

In the case of 1-chloroisoquinoline 10.2 g (62 mmol), 4-vinylphenylboronic acid 9.2 g (62 mm 〇l), tetrakis(triphenylphosphine)palladium l.〇g (〇.87 mmol) and 1,2- A mixture of 27.0 g (195 mmol) of potassium carbonate in an aqueous solution of dimethoxyethane was added and heated for 2.5 hours. The reaction mixture obtained was cooled to room temperature, and then the organic layer was extracted with ethyl acetate. After the solvent was distilled off from the extract under reduced pressure, the mixture was purified by column chromatography (solvent: chloroform / ethyl acetate = 1 0/1 mixture) to obtain a compound (a5-lH). ) 8.1 g (35 mmol) (yield 56%). (Synthesis Example 1-4: Synthesis of Compound (a4-lH)) The compound (a4-lH) was synthesized in the same manner as the compound (a5-lH) except that 1-chloroisoquinoline was changed to 2-chloroquinoline. ). -42 - 200918642 [Chem. 23]

(Synthesis Example 5: Synthesis of Compound (a7-l-H)) [Chem. 24]

Ph3PCH3Br / BunLi (a7-1-H) 7.0 g (20 mm ο 1 ) of methyltriphenylsulfonium bromide was suspended in 50 mmol of tetrahydrofuran, and then n- was added thereto at 〇 ° C 1.6 hexane solution of butyl lithium 1 2 · 3 m 1 (20 mm ο 1 ). After stirring at the same temperature for 1 hour, 5-methylindole-2-phenylpyridine was added dropwise (except that 1-chloroisoquinoline was changed to 2-chloro-5-formamidinepyridine, and 4-vinylphenylboronic acid was changed to In the same manner as the compound (a5-lH), a solution of 3.7 g (20 mmol) in 25 ml of tetrahydrofuran was stirred at room temperature for 3 hours. The solvent was distilled off from the obtained reaction liquid under reduced pressure, and purified by column chromatography (solvent: chloroform) of hydrazine gel to obtain compound (a 7 -1 - Η ) 3 . 3 g (1 8 mm ο 1 ) (yield 90%). -43- 200918642 (Synthesis Example 1-6: Synthesis of compound (b-bH)) In addition to 1-chloroiso-Salina, it was changed to 2-di--4-methyl-la-D'4-B-based basic boronic acid was changed to The compound (b 1 - 1 - Η ) was synthesized in the same manner as the compound (a5 -1 -H) except for phenylboronic acid. [Chem. 25]

(bM-H) compound (a4-2-H) and compound (b3-; lH), each according to the method described in JP-A 2007-23269 and Journal of the American Chemical Society, 1945, 67, 511. synthesis. [Chem. 26]

[Synthesis Example 2] Synthesis of Compound (α) (Synthesis Example 2 - 1 : Synthesis of Compound (α -1 )) -44- 200918642 [Chem. 27]

(α-1) A mixture of 2.5 g (15 mm〇l) of compound (bl-lH), 2.5 g (7.1 mmol) of ruthenium chloride trihydrate, 30 ml of 2-ethoxyethanol and 10 ml of water was heated for 12 hours. Still flowing. A small amount of water was added to the obtained reaction mixture, and the resulting precipitate was filtered and washed with methanol, and then dried under reduced pressure to give the compound (a-1) (3.0 g, 2.7 mmol) (yield: 76%). (Synthesis Example 2-2: Synthesis of Compound (a-2)) In addition to the compound (b 1 -1-H) was changed to dibenzo[f,h]quinoline, the compound (a-1) was used. The same method was used to synthesize the compound (a-2). [化 28]

-45- 200918642 (Synthesis Example 2 - 3 : Synthesis of Compound (α - 3 )) Synthesis of Compound (a -1 ) in addition to Compound (bl-1-H) was changed to Compound (b3-lH) In the same way, synthetic compounds (α - 3 [29]

(α-3) Compound (α-4 ) and Compound (α-5 ), according to JP-A-2006-8996, Compound (a-6) Bulletin of the Chemical Society of Japan, 1974, Vol. 47, p. 767 The method described is synthesized. -46- 200918642 [化30]

(α-5)

(α-6) [Synthesis Example 3] Synthesis of polymerizable ruthenium complex The compound (α) and the compound (L 1 - Η ) were reacted in the presence of silver trifluoromethanesulfonate to synthesize a polymerizable hydrazine. Complexes (1 -1 ), ( 1 - 2 ), (2-1), (2-2), (3-1), (4-1), (4-2) and (4-3) . A representative example thereof is a synthesis of the polymerizable ruthenium complex (1 -1) described below. a mixture of compound (α-l) 2.9 g (2.6 mmol), compound (a2-lH) 1.5 g (7.3 mmol), silver trifluoromethanesulfonate 1. 3 g (5 · 2 mmo 1 ) and toluene 1 50 ml, Heating was also carried out for 3 hours. The obtained reaction liquid is filtered with a fluorite, and the solvent is distilled off under reduced pressure, and then purified by a column chromatography method (eluting solution: toluene) of hydrazine gel to obtain a polymerizable error. Compound (1_1 ) 〇.5〇g (0.68mm〇l) (yield 13%). -47- 200918642 [化31]

2 (1-2>

-48- 200918642 Identification data of polymerizable ruthenium complexes are shown in Table 1. [Table 1] Polymeric ruthenium complex element analysis mass analysis calculation 値 measurement 値C Η Ν C Η Ν (ESI+) 1-1 63.91 4.13 5.73 64.17 4.06 5.77 733(Μ+) 1-2 65.06 3.99 5.55 65.50 4.08 5.26 757(Μ+) 2-1 66.96 5.26 4.98 67.11 5.09 4.79 843 (Μ+) 2-2 69.68 3.67 4.78 69.82 3.61 4.66 879(Μ+) 3-1 69.74 5.53 4.44 69.54 5.39 4.13 947(Μ+) 4-1 66.96 5.26 4.98 66.75 5.18 4.76 843 (Μ+) 4-2 66.30 3.62 5.39 66.46 3.47 5.25 779(Μ+) 4-3 70.04 5.13 4.46 69.90 5.17 4.68 943(Μ+) Polymeric 铱 complex (2-3) (2-4) According to JP-A-2007-23, the polymerizable ruthenium complex (3-2) is synthesized according to the method described in JP-A-2006-8996. [化32]

(2-4) (2-3) -49- 200918642

[Example 1] Synthesis of polymer compound (1 -1 ) In a sealed container, 8 Omg of a ruthenium complex (1 · 1 ), 460 mg of a polymerizable compound (El), and 460 mg of a polymerizable compound (E7) were added. Dehydrated toluene (5.0 mL) was added. Next, a 2,2 azobis(isobutyronitrile) toluene solution (0.1 M, 0.1 mL) was added, and the freeze degassing operation was repeated 5 times. It was sealed under vacuum and stirred at 60 ° C for 60 hours. After the reaction, the reaction was dropped into 200 mL of acetone to obtain a precipitate. Further, the reprecipitation purification was repeated twice with toluene-propanone, and then vacuum-dried overnight at 50 ° C to obtain a polymer compound (1-1). The weight average molecular weight (Mw) of the polymer compound (丨-1) was 42,500, and the molecular weight distribution index (Mw/Mn) was 2.62. The m/( m + n) 高分子 of the polymer compound estimated from the results of IC P elemental analysis and 13 C-N M R measurement was 0.049. Further, in the polymer compound (la), the enthalpy of x/n was 0.46, and the y/n enthalpy was 0.54. -50- 200918642

[Implementation 2), 1-2) ί Comparing I, Examples 2 to 6 and Comparative Examples 1 to 5] Polymer Compounds (2-1), (2-(3-1), (4-1), (4-2) and comparative polymer compound (, (2-3), (2-4), (3-2), (4-3) synthetic clothing complex and polymerizable compound, except Table 2 The other compounds shown in the above were operated in the same manner as in Example 1-1, and the polymers (2-1), (2-2), (3-1), (4-1), (4-2) were synthesized. And S molecular compounds (1-2), (2-3), (2-4), (3-2) -3 ) -51 - 200918642 mm VD ^Ti μ κη CO 〇ο o Ο 〇ο ο ο Ο 〇〇ο &lt;Ν κη ο κη inch Ο 〇Ό 〇Ό 〇Ό )V) »—η &gt;&lt; 〇ο C5 〇〇ο s 0.049 «η S o 2 s ο S 00 〇\ οο g 〇«—Η s ο o ο 〇ο ο 〇ο 〇ο c % CN Ό κη OS CN 卜»—Η CA &lt;Ν 卜ν〇(Ν rj ο ^-Η CN &gt; CN CN (N rn ri C4 &lt;Ν rn (Ν 〇κη Ο FM oo 88000 ο 〇\ Ο § Ο g ο κη ο ΙΤϊ 〇Ο Ο rj 9 03 1—Η inchΟ rj &gt; Η f Ν W) &amp;J3 ε s ΰ ε ε CUD CJC s ε b〇窆ε Is α inch 5 inch inch S inch gww Μ il ω] 窆ε day ο 00 toe s ε b〇6C as bJD b£ ε ε Bfi cs So tie wear S ε 〇〇ν〇β inch 5 inch inch S y inch W) inch inch S §ββ ο ο VO Ό GflTi· ^- Sww 〇o V〇s〇bO inch inch 1 Ο Ό Ξ ' ' inch § ΏΞ s^W ο νο β inch b0 inch strict ε. inch §a« ο ο ν〇VO &amp; 0 inch inch ε gww O ov〇\〇CJ) inch 々 § Ξ w ο ο ν〇ν〇 (3) Inch §Ξ« , 'W o ^o V〇TJ* bO·^* ^ S One inch chain? Total ^4π&lt;π 子杂Ci side □ ^□&lt;jn C&lt;1_ 9 杂 S&lt;Q&lt;ns side π c^&lt;n&lt;n $林蓉ci&lt;n&lt;jn 〒切蓉〇,&lt;Π&lt;Π ^n&lt;0 9 Xinlan S&lt;n&lt;n (four)Λ3 ΑΡΛ3 i as deleted by misimmunity like her &lt;Π^ΐΗ mmm &lt;〇ώώ Rh axis 4mm p□ plays iumm 4〇魍 her side η _ 憩 side π body her®&lt;〇&lt;n 辘 system □ Harmony □ _ fox acid ageing &lt ;□ rf 1·^ CN (N (N cA 4 (Ν -4 CN rn CN (Ν Ν cn CO φ 岖C4 m CO 匡 inch 匡 κη mm (N m *=> 寸 iri mn 辑 辑 镒镒镒舾 U wu JJ ii a ΛΛ -52- 200918642 "Production and Evaluation of Organic EL Elements" [Example 7 ] Use a substrate with ITO (made by NIPPO Motor Co., Ltd.). It is a substrate formed of two lines of ITO (indium tin oxide) electrode (anode) having a width of 4 mm on the other surface of a glass substrate of 25 mm square. First, on the ITO-attached substrate, poly(3,4-extended ethyldioxythiophene)·polystyrenesulfonic acid (manufactured by Bayer Co., Ltd., trade name "Beitron P") was used. The coating was performed by a spin coating method under the conditions of a number of revolutions of 3,500 rpm and a coating time of 40 seconds. Thereafter, it was dried in a vacuum dryer under reduced pressure at 60 ° C for 2 hours to form an anode buffer layer. The film thickness of the obtained anode buffer layer was about 5 Onm. Next, 90 mg of the polymer compound (1-1) was dissolved in 29 10 mg of toluene (manufactured by Wako Pure Chemical Industries, Ltd., special grade), and the solution was filtered through a filter having a pore size of 2 μm to prepare a coating. Solution. Next, the coating solution was applied onto the anode buffer layer by a spin coating method under the conditions of a number of revolutions of 30,000 rpm and a coating time of 30 seconds. After coating, it was dried at room temperature (25 ° C) for 30 minutes to form a light-emitting layer. The film thickness of the obtained light-emitting layer was about 1 0 0 n m. Next, the substrate on which the light-emitting layer is formed is placed in the vapor deposition device. Then, tantalum and aluminum were co-deposited at a weight ratio of 1:10, and in the case where the direction of extension with respect to the anode was orthogonal, a cathode having a width of 3 mm was formed into two lines. The film thickness of the obtained cathode was about 5 Onm. Finally, in an argon atmosphere, wires (wiring) were mounted on the anode and the cathode, and four organic EL elements of 4 mm in length and 3 mm in width were fabricated. On the above-mentioned -53-200918642 organic EL device, a voltage was applied by a programmable DC voltage/current source (TR6 143, manufactured by Yadbanst Co., Ltd.) to emit light. The maximum external quantum efficiency of the produced organic light-emitting device, the highest reaching luminance, and the luminance half-life when the initial luminance is l 〇〇 cd/m 2 and the current is driven by constant current are shown in Table 3. [Example 8] An organic light-emitting device was produced in the same manner as in Example 7 except that the solution used for the application of the light-emitting layer was prepared by dissolving 90 mg of the polymer compound (2-1) and 2910 mg of toluene. The maximum external quantum efficiency, the highest reaching luminance, and the luminance half-life of the organic light-emitting device produced when the initial luminance is l 〇〇 cd/m 2 and the current is driven by constant current are shown in Table 3. [Example 9] An organic light-emitting device was produced in the same manner as in Example 7 except that the solution used for coating the light-emitting layer was prepared by dissolving 90 mg of the polymer compound (2-2) and 2910 mg of toluene. The maximum external quantum efficiency, the highest reaching luminance, and the luminance half-life of the organic light-emitting device produced when the initial luminance is 100 cd/m2 and the constant current driving is shown in Table 3 are shown in Table 3. [Example 1] An organic light-emitting device was produced in the same manner as in Example 7 except that the solution used for the application of the light-emitting layer was prepared by dissolving 90 mg of the polymer compound (3-1) and 2910 mg of toluene. The organic light-emitting device produced was -54-200918642. The maximum external quantum efficiency, the highest reaching luminance, and the luminance half-life when the initial luminance is l〇〇cd/m2 and the current is driven by constant current are shown in Table 3. [Example 1 1] An organic light-emitting device was produced in the same manner as in Example 7 except that the solution used for the application of the light-emitting layer was prepared by dissolving 90 mg of the polymer compound (4-1) and 2910 mg of toluene. The maximum external quantum efficiency, the highest reaching luminance, and the luminance half-life of the organic light-emitting device produced when the initial luminance is l 〇〇 cd/m 2 and the current is driven by constant current are shown in Table 3. [Example 12] An organic light-emitting device was produced in the same manner as in Example 7 except that the solution used for the application of the light-emitting layer was prepared by dissolving 90 mg of the polymer compound (4-2) and 2910 mg of toluene. The maximum external quantum efficiency, the highest reaching luminance, and the luminance half-life of the organic light-emitting device produced when the initial luminance is l 〇〇 cd/m 2 and the current is driven by constant current are shown in Table 3. [Comparative Example 6] An organic light-emitting device was produced in the same manner as in Example 7 except that the solution used for the application of the light-emitting layer was prepared by dissolving 90 mg of the polymer compound (1-2) and 2910 mg of toluene. The maximum external quantum efficiency and the highest reaching luminance of the produced organic light-emitting device, and the luminance half-life when the initial luminance is 100 cd/m2 and the constant current driving are shown in Table 3 are shown in Table 3. -55-200918642 [Comparative Example 7] An organic light-emitting device was produced in the same manner as in Example 7 except that the solution used for coating the light-emitting layer was prepared by dissolving 90 mg of the polymer compound (2-3) and 2910 mg of toluene. . The maximum external quantum efficiency, the highest reaching luminance, and the luminance half-life of the organic light-emitting device produced when the initial luminance is 100 cd/m2 and the constant current driving is shown in Table 3 are shown in Table 3. [Comparative Example 8] An organic light-emitting device was produced in the same manner as in Example 7 except that the solution used for coating the light-emitting layer was prepared by dissolving 90 mg of the polymer compound (2-4) and 2910 mg of toluene. The maximum external quantum efficiency and the highest reaching luminance of the produced organic light-emitting device, and the luminance half-life when the initial luminance is 100 cd/m2 and the constant current driving are shown in Table 3 are shown in Table 3. [Comparative Example 9] An organic light-emitting device was produced in the same manner as in Example 7 except that the solution used for the application of the light-emitting layer was prepared by dissolving 90 mg of the polymer compound (2-3) and 2910 mg of toluene. The maximum external quantum efficiency and the highest reaching luminance of the produced organic light-emitting device, and the luminance half-life when the initial luminance is 100 cd/m2 and the constant current driving are shown in Table 3 are shown in Table 3. [Comparative Example 10] The organic light emission was produced in the same manner as in Example No. 56-200918642 except that the solution used for coating the light-emitting layer was prepared by dissolving 90 mg of the polymer compound (4-3) and 2910 mg of toluene. element. The maximum external quantum efficiency, the highest reaching luminance, and the luminance half-life of the organic light-emitting device produced when the initial luminance is 100 cd/m2 and the constant current driving is shown in Table 3 are shown in Table 3. [Table 3] ______ Maximum External Quantum Efficiency %%) Maximum Arrival Brightness (cd/m 2) Luminance Half Life (h) Example 7 7.0 45500 7000 Example 8 7.2 36200 7500 Example 9 6.9 3 1700 6900 Example 1 〇 6.8 3 3 000 73 00 Example 1 1 7.0 1 9 800 6400 Example 1 2 7.1 23 000 6600 Comparative Example 6 6.8 445 00 3 200 Comparative Example 7 7.1 32900 3 900 Comparative Example 8 6.6 32000 3 700 Comparative Example 9 6.8 3 1500 4400 Comparative Example 1 0 6.9 1 7600 3700 [Industrial Applicability] The organic EL device of the present invention is specifically suitable for use in displays, backlights, electronic photographs, illumination sources, recording light sources, exposure light sources, and reading. Light source, logo, kanban, interior, optical communication, etc. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of an organic EL device of the present invention. [Description of main component symbols] 1. Glass substrate -57- 200918642 2 : Anode 3 : Hole transport layer 4 : Light-emitting layer 5 : Electron transport layer 6 : Cathode -58

Claims (1)

200918642 X. Patent Application Range 1. A luminescent polymer compound characterized by a structural unit derived from a compound represented by the following formula (1), [Chemical Formula 1] (In the formula (1), L1 represents a ligand selected from the following formulas (al) to (a6), and L2 represents a ligand selected from the following formulas (b1) to (b6) [Chemical 2] ] (a1) (a2) (a3) -59- 200918642 [In each of the formulas (a1) to (a6), the Ra-based groups each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkyl group or a chain having 1 to 5 carbon atoms having a polymerizable functional group. In addition, one of Ra in the formula (al) to (a6) is an alkyl group or an alkenyl group having 1 to 5 carbon atoms having a polymerizable functional group as described above. 3] (b1) (b2) (b3) -60- 200918642 (b4) (b5) (b6) [In each of the formulae (b1) to (b6), Rb each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms], and 'L1 and L2 are selected. From: E1 below and E2 below satisfy the relationship of EkE2' E 1 represents a solution of a ruthenium complex represented by the following formula (2) [monochrome at a wavelength of 305 nm when the optical path length is 1 cm The absorbance of light can be measured at 25 ° C in a dichloromethane solution prepared by 〇, and the number of vibrations of light showing the maximum luminescence intensity in an luminescence spectrum excited by monochromatic light having a wavelength of 350 nm (cnT1); [Chemical 4] [In the formula (2), the L system is not in the above formula (!) [I, which is selected from one of the above-mentioned formulas -61 - 200918642 (al) to (a6), and all of the above Ra are The ligand of the hydrogen atom] E2 represents a solution of the ruthenium complex represented by the following formula (3) [when the optical path length is 1 cm, the absorbance of the monochromatic light at a wavelength of 350 nm can be 0.1 methylene chloride solution. In the luminescence spectrum excited by the monochromatic light having a wavelength of 3 5 Onm, the vibration number of the light showing the maximum luminescence intensity (c π Γ 1 ) is measured at 25 ° C; [In the formula (3), L2 is L2 in the above formula (1), which is selected from one of the above formulas (b1) to (b6), and all of the above Rb are a ligand of a hydrogen atom] ). 2. The photoluminescent polymer compound according to claim 1, wherein the polymer compound obtained by radical polymerization is a saturated carbon chain skeleton. 3. The photoluminescent polymer compound according to claim 1, wherein the difference between the Ei and the E2 is 100 or more. 4. The luminescent polymer compound according to the first aspect of the invention, wherein the luminescent polymer compound further comprises: a polymerizable compound which is transportable by a hole and a polymerizable compound which is electron transporting property - 62- 200918642 A structural unit derived from one less. 5. A method of producing an organic electroluminescence device, comprising: forming an organic compound layer containing at least one layer of a photoluminescent polymer compound according to any one of claims 1 to 4 on an anode; And a step of forming a cathode over the organic compound layer. An organic electroluminescence device comprising: a pair of electrodes; and an organic compound layer ′ including at least one of the light-emitting layers between the electrodes; and the light-emitting layer includes the first to fourth aspects of the patent application scope A light-emitting polymer compound of either of them. An organic electroluminescence device characterized in that it is manufactured according to the manufacturing method of claim 5 of the patent application. 8. A display device characterized by using the organic electroluminescent element of claim 6 or 7. -63-